PL148420B1 - Method of polymerizing or copolymerizing diolefine monomers with conjugated double bonds - Google Patents

Description

The invention relates to a process for the polymerization or copolymerization of double-linked di-olefin monomers. Rare earth catalytic systems such as lanthanide systems are usually considered to be Mpseudo-living systems. Accordingly, when polymers are produced using such rare earth catalytic systems, their molecular weight increases as the degree of conversion increases. The molecular weight of polymers made using such catalytic systems has traditionally been controlled by limiting the conversion rate and / or adjusting the level of the catalyst used. In any event, however, any change in the polymerization time or degree of conversion will affect the final molecular weight of the polymer produced. Since the residence time of the reactants in continuous polymerization systems is sometimes difficult to strictly control, polymers with different molecular weights are obtained due to the linear relationship between the molecular weight and the degree of monomer conversion. In other words, the regulation of the molecular weights of polymers produced using rare earth catalytic systems is often very difficult. In industrial scale polymerization processes, it is often highly desirable to achieve a high degree of monomer conversion. Achieving such a high degree of monomer conversion is particularly advantageous in bulk polymerization processes. On the other hand, there is a need for polymers prepared using rare earth catalytic systems with low or at most moderate molecular weights. Unfortunately, traditional molecular weight modifiers work effectively with Ziegler-Natta catalyst systems and are ineffective in polymerization processes catalyzed by rare earth systems. From US patent specification US No. 4,383,097 and South Africa Patent No. 83/2555, for example, it is known that β-olefins and uncirculated diolefins are effective chain transfer agents for use with Ziegler-Natta catalytic systems. However, cC-olefins and uncirculated diolefins are ineffective as molecular weight regulators when used with rare earth catalytic systems. The molecular weight of polymers prepared with the use of alphine catalysts can be reduced by carrying out such polymerization processes in the presence of 1,4- and 1,2-dihydronaphthalene. However, it has been found that 1,4- and 1,2-dihydronaphthalene cannot be used as molecular weight modifiers in polymerization processes using rare earth metal catalysts. based on rare earth metals. Unfortunately, the problem of molecular weight regulation can become even more complicated with the use of pre-prepared catalytic systems, since in their presence polymers of higher molecular weights are produced than in the case of non-pre-prepared catalysts. The invention is based on the unexpected finding that Vinyl halides can be used as molecular weight regulators in polymerization processes catalyzed by rare earth systems. Vinyl halides are effective as molecular weight regulators in both solution and bulk polymerization processes. Thus, the inventive method of polymerization or copolymerization of diolefin monomers with coupled double bonds using a catalytic system containing (I) an organoaluminum compound, / 2) an organometallic compound containing a metal from Group III-B of the periodic table of elements and / 3 / at least one a compound containing at least one mobile halide ion is carried out in the presence of a vinyl halide as molecular weight regulator, preferably at a temperature of about 10-90 ° C. Preferably 0.05-10 parts of vinyl halide per 100 parts of monomer. Vinyl bromide, vinyl chloride or vinyl iodide are preferably used as the vinyl halide. The invention also relates to a method of polymerizing at least one diolefin monomer with bonded double bonds in the presence of a catalytic system containing / 1 / an organoaluminium compound / 2 / an organometallic compound containing a metal from group III-B of the system of approx The invention relates to a method of polymerizing diolefin monomers having double bonds to polymers having a significant proportion of the cis-1,4 structure. The diolefins with coupled double bonds which can be polymerized according to the invention are defined by the general formula I wherein R is hydrogen, alkyl groups, including cycloalkyl groups, alkylaryl groups or aryl groups, containing 1-8 carbon atoms, and Y and Y- denote hydrogen atoms or alkyl groups containing 1-4 carbon atoms and may be the same or different. Thus, the invention relates to stereospecific polymerization of compounds, which include, but are not curative, 1,3-butadiene, isoprene , piperylene or pentadiene-1,3,2-methyl-penta-dien-1,3,2-ethylbutadien-1,3,4-butylpentadien-1,3,2,3-dimethylpentadien-1,3, hexadien- 1,3, 1,3-octadiene-1,3,1-phenylbutadiene-1,3 etc. The homopolymers of such diolefins according to the invention have more than 95% of the microstructure in 1,4 configurations. Homopolymers are non-crystalline at ambient temperature. The invention also relates to a method of polymerizing certain diolefins with certain other diolefins to form copolymers. For example, diolefins can be represented by the formula 1 where R is hydrogen, alkyl groups including cycloalkyl, alkylaryl and aryl groups containing 1-8 carbon atoms, and Y and Y are hydrogen atoms or alkyl groups containing 1 - 4 carbon atoms and may be the same or different, and may be copolymerized with interconnected diolefins as defined by formula 2, wherein Y and Y2 represent hydrogen atoms or alkyl groups with 1-4 carbon atoms. copolymerization of compounds, which include, but not cure, piperylene, i.e. 1,3,2-methylpentadiene-1,3,4-butylpentadiene-1,3,2,3-dimethylpentadiene-1,3, hexadiene-1,3 , 1,3,1-phenylpentadiene-1,3,2,3-dibutylpentadiene-1,3 and 2-ethylpentadiene-1,3, octadiene-1,3, with other linked diolefins such as 1,3-butadiene. 2-methylbutadien-1,3, i.e. isoprene, 2-ethylbutadiene-1,3, etc. 148 420 3 Copolymers of such diolefins according to the invention generally have over 90% of the microstructure in 1,4 configurations. Part of the copolymer is derived from conjugated diolefins with only 4 carbon atoms in the chain and exhibits a high degree of 1,4-cis configuration. Part of the copolymer is derived from the diolefins represented by formula 1 has a 1.4 configuration. These copolymers are usually non-crystalline at ambient temperature. The catalytic systems used in the process according to the invention consist of three components. These components are (I) an organoaluminum compound, (2) an organometallic compound containing a Group III-B metal of the Periodic Table of the Elements, and IZf at least one compound containing at least one mobile halide ion. The organoaluminum compound comprises at least one carbon-aluminum bond and may be represented by structural formula 3, wherein R 1 is an alkyl group including cycloalkyl, alkoxy, aryl, alkylaryl or aralkyl groups, or a hydrogen atom, R represents an alkyl group, including cycloalkyl, aryl, alkylaryl or aralkyl groups, or a hydrogen atom, and f-3 represents an alkyl group, including also cycloalkyl, aryl, alkylaryl or arylalkyl groups. Representative compounds corresponding to this definition include diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenyl aluminum hydride, phenyl aluminum hydride -propylaluminum, p-tolylethylaluminum hydride, p -tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propylaluminum hydride and benzyl isopropylaluminum hydride and other organic aluminum hydrides. Also included are: ethylaluminum dihydrate, butylaluminum dihydride, isobutylaluminum dihydride, octylaluminum dihydride, amylaluminum dihydride, and other organoaluminium dihydrate. These compounds also include diethylaluminum ethoxide and dipropylaluminum ethoxide, as well as trimethylaluminum, triethylaluminum, triethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, triisobutylaluminum, triethylaluminum, triethylaluminum, triethylaluminum - p-tolylaluminum, tribenzyl aluminum, ethyl-diphenylaluminum, ethyl-di-p-tolylaluminum, ethyldibenzylumin, diethylphenylaluminum, diethyl-p-tolylaluminum, diethylbenzyaluminum and other organometallic compounds of the third organometallic group. it forms a central atomic core to which ligand-type groups or atoms are attached. Such animals are sometimes called coordination-type animals. These compounds can be represented symbolically by the formula ML3 # in which M represents the above-described metal ions from the group III-B, and L represents an organic ligand containing 1-20 carbon atoms, selected from the group consisting of (1) o-hydroxyaldehydes, (2) o-hydroxyphenones, / 3 / aminophenols, / 4 / hydroxyesters, / 5 / hydroxyquinolines, / 6/4 -diphonicones, li / monocarboxylic acids, / 8 / ortho-dihydric phenolef / 9 / alkylene glycols, / lo / dicarboxylic acids, (I) alkylated derivatives of dicarboxylic acids and (I2) phenol ethers. Group III-B metals useful in organometallic compounds include akandium, yttrium, lanthanides and actinides. Lanthanides include lanthanum, cerium, praseodymium, naodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Actinides include actinium, thorium, protactinium, uranium, naptun, pluto, americium, cuur, berkel, californium, einstein, ferm, mendelev, and lawrens. The preferred actinides are thorium and uranium having atomic numbers 90 and 92, respectively. Preferred Group III-B metals are cerium, praseodymium, neodymium and gadolinium having atomic numbers 58, 59, 60 and 64 respectively. The lanthanide is neodymium. The organometallic compound used includes organic ligands or groups containing 1-20 carbon atoms. These can be monovalent and bivalent ligands or bivalent and bidentate ligands. For example, compounds which provide such organic ligands or groups include 1 o-hydroxyaldehydes such as salicylaldehyde, 2-hydroxy-1-formylnaphthalene, 2-hydroxy-3-formylnaphthalene and the like, 2 o-hydroxyphenones such as 2'- hydroxyacetophenone, 2'-o-hydroxybutyrophenone, 2'-hydroxypropiophenone, etc., 3 aminophenols such as o-aminophenol, N-methyl-o-aminophenol. N-ethyl-o-aminophenol and the like, 4 hydroxyesters such as ethyl salicylate, propyl salicylate, butyl salicylate and the like, 5 phenolic compounds, such as 2-hydroxyquinoline, 8-hydroxyquinoline, etc., 6 f-ducetones, such as acetylacetone, benzoylacetone, propionylacetone, isobutyrylacetone, valeryl- • 4 148 420 acetone, ethylacetylacetone and the like, (7) monocarboxylic acids such as acetic acid, propionic acid, valeric acid, n-caproic acid, 2-ethyl-n acid -caproic acid, neocapric acid, lauric acid, stearic acid, etc., / 8 / o-dihydric phenols such as pyrocatechin, / 9 / alkylene glycols such as ethylene glycol, propylene glycol, triiimethylene glycol, ozteromethylene glycol and the like; (10) dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, succinic acid, o-phthalic acid and the like; (11) alkylated derivatives of the above-mentioned dicarboxylic acids and (12) phenol ethers, such as as o-hydroxyanisole, o-hydroxyphenylp-ethyl ether etc. to repre Potent organometallic compounds of the group III-B metals corresponding to the formula ML4 which may be useful in the process of the invention are: cerium acetylacetonate, cerium naphthenate, cerium neocaprate, cerium caprylate, trisalicylaldehyde ether, tri (8-hydroxyquinoline) naphthenate gadolinium, gadolinium neocaprate, gadolinium caprylate, lanthanum naphthenate, lanthanum caprylate, neodymium naphthenate, neodymium neocaprate, neodymium caprylate, praseodymium naphthenate, praseodymium caprylate, yttrium bromide triethylcaprylate, yttrium trisylcaprylate / J / -allyl / uranium, tri-iodide / JT * -allyl / -urane, uranium tetramethoxide *, uranium caprylate, thorium ethoxide, tri (5T-allyl) thorium chloride, thorium naphthenate, uranium isovalerate and other group III metals B complexed with ligands containing 1-20 carbon atoms. The third component of the catalyst used in the catalytic system is a compound containing a halide ion. Some representative halide ions that may be used include bromide ions, chloride ions, fluoride ions, and iodide ions. Combinations of two or more of these ions may also be used. Such halide ions can be introduced in the form of I l and hydrogen halides, (2) metalloalkyl, -aryl, * -alkylaryl, -arylalkyl and -cycloalkyl halides, in which the metal is selected from groups II, III-A and IV- A of the periodic table, / zl of metal halides from groups III, IV, V, VI-B and VIII of the periodic table, and / 4 / organometallic halides corresponding to the general formula ML, X, in which M is a metal selected from the group consisting of metals from group III- B of the Periodic Table of atomic numbers 21, 39 and 57-71, L is an organic ligand containing 1-20 carbon atoms, selected from the group consisting of (a) o-hydroxyaldehydes, (b) o-hydroxyphenons, and c) hydroxyquinolines, / fI B -diphonic acids, / g / monocarboxylic acids, / h / o-dihydric phenols, / i / alkylene glycols, / j / dicarboxylic acids, / k) alkylated derivatives of dicarboxylic acids and / l / ethers of phenols, X is a halide ion, and y is an integer equal to 1 or 2, denoting the number of halide ions coming The organic ligand L can be monovalent and bivalent, or bivalent and bidentate. as ethylmagnesium bromide, butylmagnesium bromide, phenylmagnesium bromide, methylmagnesium chloride, butylmagnesium chloride, ethylmagnesium iodide, phenylmagnesium Joden, diethylaluminum bromide, diisobutylaluminum bromide, methylaluminum póltorabromek, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, dwuizobu¬ tyloglinu chloride, isobutylaluminum dichloride, dihexylaluminum chloride, cyclohexylaluminium dichloride, phenylaluminum dichloride, dododecylaluminum chloride, diethylaluminium fluoride, dibutylaluminium fluoride, diethylaluminium iodide, dibutylaluminum iodide, phenylaluminium dibutylchloride, tutyltinchloride tin, diphenyltin dichloride, tert-butyltin iodide and the like, (3) inorganic halides such as aluminum bromide, aluminum chloride, aluminum iodide, antimony furnace, antimony trichloride, boron tribromide, boron trichloride, ferric chloride, gallium trichloride molybdenum, phosphorus tribrach, phosphorus pentachloride, tin chloride, titanium tetrachloride, titanium tetraiodide, tungsten hexachloride and the like; and (4) group III-B organometallic halides such as salicylaldehyde chloride (IIIII) chloride, , 5-cyclohexylsalicylaldehyde acetyl chloride (III), 2-acetylphenolanacer chloride (III), oxalate chloride III, oxalate acetone bromide (III), etc. Preferred compounds containing a mobile halide ion se inorganic halogen acids and organometallic halides. 148 420 The rare earth catalyst system can be prepared either "in situ" or "pre-prepared". "In situ" means that the catalyst components are added separately to the monomer to be polymerized. "Pre-treatment" means that the catalyst components are mixed together prior to exposing any of the components to the polymerized monomer. It is known that when using the catalyst systems of the type described herein, the presence of monomer is not necessary for the formation of active catalytic sites, which greatly facilitates the use of "pre-prepared" catalysts. It is also known that freshly "pre-prepared" 8a catalysts are often more active than catalysts. which were subjected to aging prior to use. Significantly improved "pre-prepared" catalysts can be obtained by "pre-preparation" in the presence of small amounts of double coupled diolefins. Pre-treatment in the presence of monomers results in homogeneous (soluble) catalytic systems, whereas systems obtained by mixing without the presence of monomers are often heterogeneous (insoluble). Such a "preconditioning" method is described in detail in US Patent No. US No. 3,794,604. The proportions of the components in the polymerization catalyst systems according to the invention can be varied within wide ranges. If the halide ion in the halogen containing compound is bromide, chloride or iodide, the atomic ratio of the halide ion to the Group III-B metal may vary from about 0.1% to about 6/1. More preferably, the ratio is from about 0.5 / 1 to about 3.5 / 1 and most preferably from about 2/1. The ratio of fluoride ion to Group III-B metal ion is from about 20/1 to about 80/1, and most preferably from about 30/1 to about 60/1. The molar ratio of aluminum trialkyl or aluminum alkyl hydride to Group III-B metal may range from about 4/1 to about 200/1, most preferably from about 8/1 to about 100/1. The molar ratio of the diolefin to the Group III-B metal may range from about 0.2 / 1 to about 3000/1, most preferably from about 5/1 to about 500/1. reactionary can vary widely. All that is required is that a catalytic amount of catalytic system sufficient to cause polymerization of the diolefin is present in the reaction system. Low catalyst concentrations are recommended to reduce ash problems. It has been found that polymerization proceeds when the catalytic level of the Group III-B metal is between about 0.05 and 1.0 millimoles per 100 g of monomer. Preferably, the ratio is 0.1 to 0.3 millimoles of Group III-B metal per 100 g of monomer. The total concentration of the catalytic system used will, of course, depend on factors such as system purity, the desired polymerization rate, temperature, and other factors. For this reason, it is not possible to pre-specify specific concentrations, but it can only be stated that catalytic amounts are used. The polymerization of the diolefin can be carried out by bulk or solution polymerization using suitable inert solvents. The term "inert solvent" means that the solvent is not incorporated into the structure or adversely affected by the polymer produced. Solvents such as, usually, aliphatic, aromatic and cycloaliphatic hydrocarbons, which include, for example, pentane, hexane, heptane, benzene, toluene, cyclohexane, etc. The volume ratio of the solvent to monomer can vary widely. The ratio of the volume of solvent to monomer may be from greater than 1 to 20. However, it is usually preferred or convenient that the ratio of solvent to monomer is from about 3/1 to about 6/1. In bulk polymerization processes, the reaction medium is substantially solvent-free and contains no more than about 10% organic solvent compounds of the polymer produced, based on the total weight of the reaction mixture. In most cases, the reaction medium contains less than 4% by weight of solvents or virtually no solvents. The temperature at which the polymerization reactions are carried out can vary over a wide range. Typically, the temperature may range from very low temperatures of -60 ° C to high temperatures of 150 ° C or more. Therefore, temperature is not a critical factor in the process of the invention. In general, however, it is preferable to carry out the reactions at a temperature ranging from about 10 to about 90 ° C. The pressure at which the polymerization is carried out may also vary widely. Reactions can be carried out under atmospheric pressure or, if necessary, they can be carried out at less or greater than atmospheric pressure * Usually, the course of polymerization is satisfactory if the reactions are carried out at a pressure close to the autogenous pressure produced by the reactants under the conditions prevailing during the process * Oo Vinyl halides that can be used as molecular weight regulators include vinyl fluoride, vinyl chloride * vinyl bromide *! vinyl iodide * Preference is given to using vinyl bromide * vinyl chloride and vinyl iodide. In general, vinyl chloride and vinyl bromide are most preferably used. The amount of vinyl halide used varies according to the desired molecular weight of the polymer produced. Of course, by using more vinyl halide, a polymer with a lower molecular weight is obtained. As a rule, from about 0.05 to 10 parts of vinyl halide per 100 parts of monomer are used. In most cases, 0.1 to 2.5 parts of vinyl halide per 100 parts of monomer are used in the polymerization process. Those skilled in the art will readily determine the amount of vinyl halide necessary to obtain a polymer of a specific molecular weight * logarithmic viscosity number, Mooney viscosity, numerical average molecular weight (Mn) and weight average molecular weight (M). 5 wt.% In toluene * Mooney viscosity was determined using a large rotor, a one-minute preheating time and a four-minute measuring time at 100 ° C. The indicated numerical and weight average molecular weights were determined using a Waters GPC Model No. 150C gel chromatograph and using polymers dissolved in chloroform. Examples 1-9 A solution of butadiene in hexane was passed through the column containing If the silica gel was in the form of a powder, weighed amounts of the solutions were put into a series of bottles with a capacity of 118 ml. The solutions were purged with dry nitrogen for 25 seconds. Each bottle contained approximately 10 g of butadiene per 100 ml of solution. Increasing amounts of the three potential molecular weight modifiers were introduced into each of these solutions, except for the first used as control solution, as indicated in column 3 of Table 1. The catalyst components were incorporated into each bottle in situ "in the following order: a / 0.92 ml of 0.89-m solution of triisobutylaluminum / TIBAL / in hexane, b / 0.43 ml of 0.058 ml of neodymium 2-ethyl-n-caproate / Nd Oct / ic / 0.10 ml of 0.25 m solution of ethyl aluminum dichloride / EADC / in hexane. The bottles were then tightly closed using a rubber insert and a Teflon seal. The bottles were placed in a water bath with a regulated temperature of 50 ° C and rotated in a vertical plane for a period of time shown in Table 1. The polymerization was stopped by injecting 0.05 g of 2,4-6-tri (dimethylaminomethyl) -phenol, 0.1 g of dibutyl-p-cresol and 0.5 ml of methanol in hexane. The polymer solutions were placed on ply Petrie and dried first in air and then under reduced pressure. The addition of 2,500-10,000 parts per million of vinyl chloride to butadiene causes a reduction in the molecular weight of the polybutadienes obtained, as evidenced by log viscosity numbers (DSV) and average molecular weight by weight determined by the gel chromatography method, given in columns 6 and 7 of Table 1, in which the dash, like in other tables, means that the given determination was not performed. It turned out that chloroethane and 1,4 dihydro-naphthalene were not effective as molecular weight modifiers. 148 420 Table 1 Example 1 I 1 IJ 1 11Z 1 IV 1 V 1 VI 1 VII 1 VIII 1 IX Potential molecular weight modifier Name Control sample Without regulator Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Chloroethane Chloroethane 1,4-Dihydronaphthalene 1,4-Dihydronaphthalene Amount / ppm / in butadiene ". 0. 1000 2500 5000 10000 1000 10000 2500 10000 Polymerization time / hours / 1 2 2 2 2 2 4 2 2 Polymer yield / wt% / 48 68f4 69.5 68 64 66.5 62.6 66 56 DSV / dl / g / 4.64 4.66 4.32 3.54 3.68 4.65 I 4.94 4.58 4.51 M × 10 "3 Weight average Molecular race *" and 746 1,682,634 1,669 1 - - and 1 Examples X-XI. Homogeneous "pre-prepared" catalysts were obtained in the presence of butadiene as follows. 12 ml of a 2.45 m solution of anhydrous butadiene in hexane was injected with a syringe into a dry 118 ml nitrogen purged glass bottle with a magnetic stir bar stalk placed therein. Then 37.2 ml of a 1.2 M solution of diisobutylaluminum hydride in hexane was introduced into the bottle, 5.2 ml of a 0.66 M solution of neodymium 2-ethyl-n-caproate in hexane was slowly injected into the bottle, stirring the contents of the bottle and cooling briefly in a beaker ice-water, then 13.4 ml of a 0.25 M solution of ethyl aluminum dichloride were slowly injected while stirring the contents of the bottle. This catalyst solution (A) was allowed to stand for 3 hours at room temperature before being used in further experiments. 6.95 g of vinyl chloride was injected with a syringe into a stoppered 118 ml bottle containing 48.57 g of anhydrous hexane. This was calculated to correspond to a concentration of 8.58% w / v vinyl chloride in hexane. Then 3.3 ml of catalyst A preform solution was injected into a dry nitrogen purged bottle to which 8 ml of vinyl chloride in hexane solution was then added to determine if the precooked catalyst would remain active if stored in the presence of vinyl chloride. This solution was labeled as Catalyst B. 100 ml. Aliquots of anhydrous butadiene solution in hexane, containing 13.3 g of butadiene, were added to each of the 7 bottles of 118 ml. The first bottle was used for the control run. Increasing amounts of a solution of vinyl chloride in hexane, ranging from 1,000 to 25,000 parts per million vinyl chloride based on the weight of butadiene, were injected into the five bottles containing butadiene in hexane by means of a syringe. 0.66 ml of the pre-prepared Catalyst A solution was then injected into each of the six bottles containing the premix. 2.3 ml of catalyst B solution was injected into a seventh bottle, fresh stoppers were used to seal the bottles which were then rocked vertically at 50 ° C in a water bath for 1 hour, except for the bottle of Example 15 which was left on the surface. 70 minutes. The polymerizations were stopped as in Examples 1-9. The results are given in Table 2.8 148 420 Table 2 Example No. 1 X 1 XI 1 XII 1 XIII 1 XIV 1 XV 1 XVI Vinyl chloride / ppm / 0 1000 2500 5000 10000 25000 10000 Catalyst AAAAAAB Polymer yield /% by weight / 87 87.5 85 86 81 85 80 DSV / dl / g / 2.58 1 2.27 1 "2.28 1 2.14 | 2.23 1 2.28 1 Examples XVII-XXVI. A homogeneous" pre-prepared "catalyst was obtained the presence of butadiene as follows: 60 ml of a 2.2 M solution of butadiene in hexane was injected with a syringe into a dry 240 ml nitrogen-purged bottle, then with 94.5 ml of a 2.2 M diisobutylaluminum hydride / DIBA solution. -H / in hexane, slowly injected 12.3 ml of a 0.66 M solution of neo-smoke 2-ethyl-n-caproate in hexane while stirring the contents of the bottle with a magnetic stirrer, followed by slow injection of 32.4 ml of a solution of ethylaluminum dichloride in hexane. hexane, stirring the contents of the bottle and cool it slightly. This catalyst solution was allowed to stand at room temperature for 3 6 days before using it in the experiments described below. 100 ml aliquots of anhydrous butadiene in hexane, containing 13.5 g of butadiene, were dispensed into each of a series of 118 ml bottles. Five unsaturated hydrocarbons ranging from 1,000 to 25,000 ppm were injected into the butadiene-hexane solutions. The mixture was diluted with hexane to a 5-7% w / v solution prior to injection into the hydrocarbon premix. Then, 3 ml or 4.55 g of vinyl bromide was injected into a bottle containing 65 ml of natural hexane to give a 6.8% w / v solution of vinyl bromide in hexane. Appropriate amounts of this solution were injected into the butadiene (Bd) solution in hexane until the concentrations indicated in column 2 of Table 3 were obtained. the bottles were closed with a fresh stopper and liner. The concentration of the catalyst components was about Bd / DIBA-H / NdOct / EADC = 4 / 3.35 / 0.24 / 0.24 / millimoles / 100 g of butadiene. All bottles were placed in a controlled-temperature water bath of 50 ° C and a water bath. They were sprayed in a vertical plane for 1 hour, with the exception of the bottles of Examples XXII and XXVI, the contents of which were polymerized for 2.5 and 2 hours, respectively. The polymerization was stopped with 2,4,6-tri (dimethylaminomethyl) phenol, isopropanol and dibutyl-p-cresol. The addition of vinyl bromide to butadiene reduces the molecular weight of polybutadiene produced in its presence, as evidenced by the results of DSV determinations. and the number averages and weight averages of molecular weights given in Table 3. Other unsaturated hydrocarbons, such as p-bromostyrene, vinylidene chloride, 2-chloropropene and 2-chlorobutene-2, were not effective. 148 420 9 Table 3 Example No. 1 XVII 1 XVIII 1 XIX 1 XX 1 XXI 1 XXII 1 XXIII 1 XXIV 1 xxv 1 XXVI Appendix Name Control test Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide p-Bromostyrene Vinylidene chloride 2-Chloropropene 2-Chlorobutene Quantity / ppm / w butadiene o 1000 2500 5000 10000 25000 2500 2500 2500 2500 Weight of polymer / g / 9.51 8.43 7.43 6.90 6.55 8.60 8.75 9.39 8.11 9.24 DSV 1 / dl / g / 7'5 6.5 6.8 6.0 5.8 4.9 7.6 7.6 7.9 7.2 Molecular mass 1 x 10 -3 1 Mn 1 ¦'482 1 208 1 270 314 232 180 - - - - Mw 1 1194 1 1070 1 1075 1 1057 1 1008 1 903 1 1 1 1 • I Examples XXVII-XXXI. Pure butadiene was polymerized in the presence of vinyl bromide in amounts large enough that the Mooney viscosities of the resulting polybutadienes could be determined. About 100 g of butadiene for rubber production was introduced into each of a series of dry, nitrogen-purged, tared 950 ml glass bottles in which magnetic stirring sticks were placed and then closed with perforated metal nuts with rubber inserts. About the butadiene was injected with a syringe. increasing amounts of vinyl bromide. The catalyst components were introduced "in situ" by injecting / l / 1.75 ml of 1.2 m solution of diisobutylaluminum in hexane / 2 / 1.0 ml of 0.10 m solution of neodymium neocaprate in hexane sledges and / 3 / 0.4 ml of 0.25 m solution of ethyl aluminum dichloride in hexane to butadiene in each of the bottles, the contents of which were mixed simultaneously with a magnetic stirrer. The bottles were then placed in polyethylene containers containing warm water at a temperature of 48 ° C, on magnetic stirrers for a period of 1 hour. The precursors of the stirrers stopped turning after about 13-23 minutes due to the formation of an almost solid polymer. The bottles containing the contents were very hot, although the temperature of the water mantle did not reflect this because in fact during this hour the water had cooled to 44 ° C. The polymerizations in Examples XXVII-XXX were completed after 1 hour, and in Example XXXI after 1.75 hours. injecting 24 ml of hexane solution containing 1.2 g of 2,4,6-tri (dimethylaminomethyl) phenol and dibutyl-p-cresol into each of the polymers. The results given in Table 4 indicate a sharp reduction in molecular weight. polymers produced in the presence of vinyl bromide. The method of infrared spectroscopic analysis also examined the microstructures of the polymers from Examples XXVII and XXXI, showing 98% poly (1,4-cis-butadiene, 1% poly) respectively. trans-1,4-butadiene and 1% polybutadiene-1,2 and 97% poly (cis-butadiene-1,4), 1% poly (trans-1,4-butadiene) and less than 1% polybutadiene-1 , 2. This means that the microstructure is not significantly affected by vinyl bromide. Examples XXXII-XXXIII. Pure butadiene was polymerized in slightly larger amounts by introducing approximately 900 g of anhydrous liquid butadiene into a 2.5 liter horizontal cylindrical steel reactor. It was a laboratory kneader-reactor sealed with a flange plate through which a high-torque mechanism was connected to the agitator shaft. A glass plate or sight glass covered the other end of the cylinder. A cylindrical heating mantle was placed around the cylindrical reactor to allow the monomer to be heated to 50 ° C before initiating the bulk polymerization reaction. 10 148 420 Table 4 Example 1 No. 1 XXVII 1 XXVIII 1 XXIX 1 XXX | XXXI Batch / g / Butadiene 99.6 100 99.6 100 100, Vinyl bromide 0 0.55 1.0 2.15 5.5 Weight of polymer / g / 80.7 83.4 80.5 84.5 70, 5 DSV / dl / g / 4.9 2.7 2.8 2.5 2.6 Mooney Viscosity 56 37 33 31.5 30 Molecular Weight x 10 ~ 3 1 Mn 87 56 59 72 | 65 1 "" 1,635 1,438 1,410 1,432 1,397 1 Vertically cylindrical tubing containing cooling spirals was mounted at the top of the reactor cylinder. Butadiene and other monomers or desired hydrocarbons were introduced into the reactor by "injecting" them through the line leading to the bottom of the column and to the top of the reactor. The catalyst was then introduced through the same line. The cooling agent was toluene, which was expressed in a bath containing dry ice and acetone and then passed through cooling coils in a closed circuit. Vapors of monomers and other hydrocarbons condensed in the cooling column and flowed back to the reactor. The pressure in the reactor (a uniformly and the temperature) was regulated at the level of 0.590 ± 0.014 MPa and 50 + 2 ° C, respectively, by manually adjusting the pumping rate of the coolant. The second conduit also reached the bottom of the reflux cooler and the top of the reactor. polymer stabilizers, chain breaker and antioxidant to the reactor when the polymerization was to be completed. Mixing was provided by cross-disc-shaped elements mounted on a rotating horizontal shaft, provided with mixing and kneading rods. About the inner wall of the cylinder, in the areas not ridden by the mixing and kneading bars, two rows of two stationary anti-knife blades were installed. The paddles were mounted to scrape and clean the agitator shaft and the disc-shaped elements placed on it. The joint interaction of the rotating disks and mixing rods with anti-lamellae ensured good kneading and mixing of the viscous polymer and catalyst, and then also the polymer with stabilizers, and, at the same time, self-cleaning of the metal surfaces. In order to initiate the polymerization, a pre-prepared catalyst was introduced into the reactor. The pre-prepared catalyst was obtained in a dry glass bottle with a capacity of 118 ml, with a magnetic stirrer stalk placed in it, introducing 1.0 ml of 2.45 ml of butadiene solution in hexane / 2/23.4 ml of 1.2 m solution of diisobutylaluminum hydride in hexane (3) 4.3 ml of 0.66 mm solution of neodymium 2-ethyl n-caproate in hexane and (4) 11.2 ml of 0.25 ml solution of ethyl aluminum dichloride in hexane . Then 39 ml of freshly prepared catalyst was drawn into a syringe and introduced into a small, dry, nitrogen-purged steel bomb. The pre-prepared catalyst solution was then injected into the cylindrical reactor under nitrogen pressure. Polymerizations were continued until the plate? glass, it was possible to see only one phase / constant /. The polymerization was stopped by injecting about 5 ml of isopropanol into the reactor under nitrogen pressure and a solution containing 7 ml of tri (dimethylaminomethyl) phenol and 6.75 g of dibutyl-p-cresol in 200 ml of liquid butadiene. for about 10 minutes, the pressure in the reactor was gradually released, allowing the unpolymerized hydrocarbons to evaporate. The resulting polymer was then dried under a vacuum of 6.67 kPa and a temperature of about 50 ° C. for at least 15 hours. In Example XXXII, the test experiment, 732 g of polymer was obtained, corresponding to a conversion rate of 81.5%. The test for Example XXXIII was carried out in a very similar manner, except that after the introduction of butadiene into the reactor, it was injected under nitrogen pressure. g of vinyl chloride, before heating the contents of the reactor to 50 ° C and before adding the catalyst. The comparison of the results presented in Table 5 shows the effect of vinyl chloride on the reduction of the molecular weight of the polymer. Examination of the microstructure of the polymer prepared in Example XXXIII by the infrared analysis method showed 96% poly (cis-butadiene-1, ^%, 1% poly (1,4-trans-butadiene) and less than 1% polybutadiene-1,2. It was stated in connection with tyra that vinyl chloride does not affect the polymer microstructure Table 5 1 Example No. XXXII 1 XXXIII Batch / g / Butadiene 899 897 Vinyl chloride 0 19 Polymerization time / minutes / 16.5 13.0 Polymer yield / g / 732 666 Mooney Viscosity * a. 107 57 | DSV l / dl / g / 3f3 2.8 Molecular weight x 10 "3 Mn 181 130 Mw 1 562 443 1 Examples XXXIV-XLI. A premix solution was prepared containing approximately 133 g of isoprene per 1 liter of hexane solution, then passed through the column filled with silica gel and purged with nitrogen. 100 ml aliquots of this solution were put into 8 vascular 118 ml bottles. The precooked catalyst was prepared in the same way and with the same proportion of components as in Examples XXXII and XXXIII. Table 6 Example 6 Example No. XXXIV 1 XXXV 1 XXXVI [XXXVII 1 XXXVIII XXXIX 1 XL XLI Specified halide Amount (ppm) in relation to isoprene 0 2500 5000 10000 2500 5000 10000 10000 Name control test vinyl chloride vinyl chloride vinyl chloride vinyl bromide vinyl bromide vinyl bromide of benzyl Efficiency /% wt / 36 35 36 36 36 30 27 36 DSV / dl / g / 5.35 5'2 1 5.1 | 4.8 | 5.6 1 4'7 1 4.5 | 'Quantities of organic halides listed in the second column in Table 6 of the introduction They were injected as solutions in hexane as described in Examples X-XVI into bottles containing a premix of isoprene in hexane. Then 0.58 ml of the pre-prepared catalyst were injected. This amount corresponded to the catalyst charge Bd / DIBA-H / NdOct / EADC = = 2 / 2.5 / 0.25 / 0.25 mmoles per 100 g of isoprene. The bottles were closed with stoppers and placed in a polymerization bath regulated at 50 ° C, and then rocked in a vertical plane. As the polymerization progressed, a sticky putty formed in all bottles, except for the bottle into which the benzyl chloride was added. In this case, polyisoprene was insoluble in hexane and its small solid particles swayed in the semi-suspension. The polymerization was stopped after 4 hours (after 16 hours in Example XLI) by adding 0.06 g of 2,4,6-tri (dimethylaminomethyl) phenol and 0.12 g of dibutyl-p-cresol as a solution in hexane. The data presented in the last column of Table 6 confirms that the presence of both vinyl chloride and vinyl bromide during polymerization results in a reduction in molecular weight (DSV) of the resulting polyisoprenes. The vinyl halides did not affect the polymer microstructure. On the other hand, the addition of benzyl chloride resulted in the formation of numerous radicals, which caused the cyclization of polisoprene. Patent claims 1. Method of polymerization or copolymerization of diolefin monomers with interconnected double bonds, especially in mass or in solution, with the use of a catalytic system containing an organo-aluminum compound, containing a metal from Group III-B of the element system and at least one compound containing at least one mobile halide ion, characterized in that the process is carried out in the presence of a vinyl halide as molecular weight regulator, preferably at a temperature of about 10-90 ° C. C. 2 * Method according to claim lf characterized in that 0.05-10 parts of vinyl hacogenide is used per 100 parts of monomer. 3. The method according to p. The method of claim 1, wherein the vinyl halide is vinyl bromide, vinyl chloride or vinyl iodide. HX = CC = CH-R IIY, Y2 Formula 1 H = C- C = CH2 II Yi Y2 Formula 2 Al ^ - R2 " * 3 Model 3 Printing House of the Polish Patent Office, Mintage 100 copies Price PLN 1,500 PL PL

Claims (3)

1. Claims 1. A method of polymerization or copolymerization of diolefin monomers with interconnected double bonds, especially in mass or in solution, using a catalytic system containing an organoaluminum compound, an organometallic compound containing a metal from group III-B of the elemental system and at least one containing at least one mobile halide ion, characterized in that the process is carried out in the presence of a vinyl halide as molecular weight regulator, preferably at a temperature of about 10-90 ° C. 2. * Method according to p. lf characterized in that 0.05-10 parts of vinyl hacogenide is used per 100 parts of monomer. 3. The method according to p. The process of claim 1, wherein the vinyl halide is vinyl bromide, vinyl chloride or vinyl iodide. HX = C-C = CH-R I I Y, Y2 Pattern 1 H £ = C- C = CH2 I I Yi Y2 Pattern 2 Al ^ - R2 "* 3 Pattern 3 Printing Workshop of the UP RP. Circulation 100 copies. Price PLN 1500 PL PL